CN112694726A - Modified PGA material with higher processing performance and preparation method thereof - Google Patents
Modified PGA material with higher processing performance and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000012545 processing Methods 0.000 title abstract description 36
- 229920000954 Polyglycolide Polymers 0.000 claims abstract description 89
- 239000004633 polyglycolic acid Substances 0.000 claims abstract description 87
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000004014 plasticizer Substances 0.000 claims abstract description 40
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 27
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 27
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 11
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- 239000002994 raw material Substances 0.000 claims abstract description 11
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- 238000000034 method Methods 0.000 claims description 15
- 230000009477 glass transition Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 208000016261 weight loss Diseases 0.000 claims description 7
- 230000004580 weight loss Effects 0.000 claims description 7
- 230000005484 gravity Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920001896 polybutyrate Polymers 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention provides a modified PGA material with higher processing performance and a preparation method thereof, wherein the modified PGA material is prepared from the following raw materials: 5-15 parts of plasticizer, 70-80 parts of polyglycolic acid and 5-25 parts of compatilizer; the molecular weight of the polyglycolic acid is 30-50 ten thousand g/mol; the plasticizer is a mixture of polyvinyl alcohol and ethylene glycol, the molecular weight of the polyvinyl alcohol is 500-800 g/mol, and the alcoholysis degree is 88-95%; the epoxy equivalent of the compatilizer is 280-310 g/mol, and the molecular weight is 8000-10000 g/mol. The invention adopts the specific types of plasticizers and compatilizers to modify the polyglycolic acid, so that the polyglycolic acid has lower melting point and higher processing rheological property; and has better compatibility with other materials.
Description
Technical Field
The invention belongs to the technical field of PGA modified materials, and particularly relates to a modified PGA material with higher processing performance and a preparation method thereof.
Background
PGA (polyglycolic acid), also called polyglycolide, is the highest degradation speed in aliphatic polyester materials because of the shortest repeating unit in the molecular structure, and meanwhile, the low molecular weight product is an ideal complete microbial degradation inducer. From the viewpoint of the chemical structure of the polymer, the ideal completely biodegradable plastics are mainly degradable aliphatic polyesters, which have completely decomposable ester groups in the chemical structure. The completely degradable polyesters have the characteristics of microbial degradation and water degradation, are non-toxic and harmless, and the final decomposition products are carbon dioxide and water, so the completely degradable polyesters are environment-friendly materials and biodegradable materials recognized in the world.
However, the PGA material has a high melting point and hardness due to the short repeating units, weak segment movement ability and high ester group density, and the processing rheological property is greatly influenced.
Disclosure of Invention
In view of the above, the present invention is directed to a modified PGA material with high processability and a method for preparing the same.
The invention provides a modified PGA material with higher processing performance, which is prepared from the following raw materials:
5-15 parts of plasticizer, 70-80 parts of polyglycolic acid and 5-25 parts of compatilizer;
the molecular weight of the polyglycolic acid is 30-50 ten thousand g/mol;
the plasticizer is a mixture of polyvinyl alcohol and ethylene glycol, the molecular weight of the polyvinyl alcohol is 500-800 g/mol, and the alcoholysis degree is 88-95%;
the epoxy equivalent of the compatilizer is 280-310 g/mol, and the molecular weight is 8000-10000 g/mol.
Preferably, the mass ratio of the polyvinyl alcohol to the ethylene glycol is 1: 0.9 to 1.1.
Preferably, the plasticizer is prepared according to the following method:
drying polyvinyl alcohol and ethylene glycol at 63-68 ℃ for 5.5-6.5 h, and mixing for 25-35 min to obtain the plasticizer.
Preferably, the PGA has a melting point of 220-230 ℃, a glass transition temperature of 38 + -5 ℃, and a specific gravity of 1.2-E1.3g/cm3。
The invention provides a preparation method of a modified PGA material with higher processing performance, which comprises the following steps:
and (3) mixing 5-15 parts of plasticizer, 70-80 parts of polyglycolic acid and 5-25 parts of compatilizer for 30-60 min, and extruding and granulating to obtain the modified PGA material with high processability.
Preferably, the weight loss water content of the plasticizer, the polyglycolic acid and the compatilizer after mixing is 1.5-2%.
Preferably, the aspect ratio of the extrusion granulation is greater than 1: 55.
preferably, during the extrusion granulation, the temperature of the feeding section is 165-175 ℃, the temperature of the mixing section is 225-235 ℃, and the temperature of the extrusion section is 185-195 ℃.
Preferably, the extrusion granulation adopts an underwater granulation mode.
The invention provides a modified PGA material with higher processing performance, which is prepared from the following raw materials: 5-15 parts of plasticizer, 70-80 parts of polyglycolic acid and 5-25 parts of compatilizer; the molecular weight of the polyglycolic acid is 30-50 ten thousand g/mol; the plasticizer is a mixture of polyvinyl alcohol and ethylene glycol, the molecular weight of the polyvinyl alcohol is 500-800 g/mol, and the alcoholysis degree is 88-95%; the epoxy equivalent of the compatilizer is 280-310 g/mol, and the molecular weight is 8000-10000 g/mol. The invention adopts the specific types of plasticizers and compatilizers to modify the polyglycolic acid, so that the polyglycolic acid has lower melting point and higher processing rheological property; and has better compatibility with other materials.
Drawings
FIG. 1 is an SEM image of unmodified conventional PGA material blended with PBAT;
FIG. 2 is an SEM photograph of the modified PGA prepared in example 1 according to the present invention after being blended with PBAT.
Detailed Description
The invention provides a modified PGA material with higher processing performance, which is prepared from the following raw materials:
5-15 parts of plasticizer, 70-80 parts of polyglycolic acid and 5-25 parts of compatilizer;
the molecular weight of the polyglycolic acid is 30-50 ten thousand g/mol;
the plasticizer is a mixture of polyvinyl alcohol and ethylene glycol, the molecular weight of the polyvinyl alcohol is 500-800 g/mol, and the alcoholysis degree is 88-95%;
the epoxy equivalent of the compatilizer is 280-310 g/mol, and the molecular weight is 8000-10000 g/mol.
The invention adopts the specific types of plasticizers and compatilizers to modify the polyglycolic acid, so that the polyglycolic acid has lower melting point and higher processing rheological property; and has better compatibility with other materials.
The modified PGA material provided by the invention comprises 5-15 parts of plasticizer; the plasticizer is a mixture of polyvinyl alcohol and ethylene glycol, the molecular weight of the polyvinyl alcohol is 500-800 g/mol, and the alcoholysis degree is 88-95%. The mass ratio of the polyvinyl alcohol to the ethylene glycol is preferably 1: 0.9 to 1.1, and more preferably 1: 1. The polyvinyl alcohol needs to control molecular weight and alcoholysis degree, the plasticizing effect cannot be achieved due to low molecular weight, and the friction force between PGA chain segments is large. Polyvinyl alcohol having an excessively large molecular weight affects the phase size of PGA blending, and also is disadvantageous in terms of processing. The 88% alcoholysis level was used primarily to improve the compatibility of the plasticizer itself with the PGA material. In the specific embodiment, the adopted polyvinyl alcohol is polyvinyl alcohol with alcoholysis degree of 88% and molecular weight of 800; or polyvinyl alcohol with 95 percent of alcoholysis degree and 800g/mol of molecular weight; the ethylene glycol is industrial grade ethylene glycol.
In the present invention, the plasticizer is preferably prepared according to the following method:
drying polyvinyl alcohol and ethylene glycol at 63-68 ℃ for 5.5-6.5 h, and mixing for 25-35 min to obtain the plasticizer.
The modified PGA material provided by the invention comprises 70-80 parts of polyglycolic acid (PGA); the molecular weight of the polyglycolic acid is 30-50 ten thousand g/mol; the molecular weight of the polyglycolic acid can ensure the mechanical property and the use shelf life of the PGA, the PGA with excessively high molecular weight is not beneficial to cost control and difficult to process, and the PGA with excessively low molecular weight has insufficient mechanical property and short use shelf life, so that the PGA cannot be applied on a large scale.
In the present invention, the PGA preferably has a melting point of 220 to 230 ℃, a glass transition temperature of 38. + -.5 ℃ and a specific gravity of 1.2 to 1.3g/cm3The ash content is preferably less than 0.05%. In a specific embodiment, the molecular weight of the PGA is 35 ten thousand g/mol or 30 ten thousand g/mol.
The modified PGA material provided by the invention comprises 5-25 parts of compatilizer; the epoxy equivalent of the compatilizer is 280-310 g/mol, and the molecular weight is 8000-10000 g/mol. The compatibilizer is preferably a commercially available compatibilizer. The compatilizer can graft PGA, so that the plasticizing effect of the plasticizer is increased, and the stabilizing effect on the melt index and the mechanical property of the PGA is achieved. The compatilizer is ADR resin produced by Basff; in a specific embodiment, the epoxy equivalent of the compatilizer is 280, and the molecular weight is 10000 g/mol; or the epoxy equivalent of the compatilizer is 300 and the molecular weight is 8000 g/mol.
The invention provides a preparation method of a modified PGA material with higher processing performance, which comprises the following steps:
and (3) mixing 5-15 parts of plasticizer, 70-80 parts of polyglycolic acid and 5-25 parts of compatilizer for 30-60 min, and extruding and granulating to obtain the modified PGA material with high processability.
According to the method provided by the invention, the environment-friendly plasticizer is added for grafting and blending, the water content of the material is controlled, and the modified PGA material prepared by combining the process conditions has a lower melting point and a higher processing rheological property; the addition of the compatilizer enables the compatilizer to be better compatible with other materials; and the energy is saved and the environment is protected.
In the invention, the weight loss water content of the plasticizer, the polyglycolic acid and the compatilizer after mixing is 1.5-2%. According to the invention, the material obtained by mixing the plasticizer, the polyglycolic acid and the compatilizer is preferably dried for more than 12 hours under the conditions of the relative humidity of 25% and the temperature of 25-30 ℃ to meet the requirement of weight loss and water content, otherwise the requirement of the melt index in the actual processing process cannot be met.
In the present invention, the aspect ratio of the extrusion granulation is at least 1: 55.
In the invention, during extrusion granulation, the temperature of the feeding section is 165-175 ℃, the temperature of the mixing section is 225-235 ℃, and the temperature of the extrusion section is 185-195 ℃. And the extrusion granulation adopts an underwater granulating mode. And drying the master batch obtained by extrusion granulation for 110-130 min at 75-85 ℃, packaging by adopting an aluminum foil, vacuumizing, and storing in a dry environment.
Melting point and glass transition temperature are important indicators for the rheological processability of the resin. Too high a melting point will increase the energy consumption during processing, and at the same time, the melting point will increase the melting temperature and decomposition temperature of the material too close to each other, which is not good for processing the material. The glass transition temperature reflects the lowest temperature of the movement of the high molecular chain segment, the material can hardly reach a viscous state due to higher glass transition temperature, and the material is not easy to be compatible with other materials in the processing process, so that the overall mechanical property is influenced.
The melting point and the glass transition temperature of the PGA material are measured by a DSC (differential thermal scanner) through heat absorption and heat release in the process of temperature change of the material.
The invention adopts a torque rheometer to measure the processing torque by monitoring the stress of the rotor in the processing process.
The crystallization behaviour of the blends was investigated by DSC, using pure indium to correct the baseline at 10 deg.C/min, and the test was carried out under a nitrogen blanket of 50 ml/min. Approximately 8mg of sample was placed in a sealed aluminum crucible and first warmed from room temperature to 200 ℃ at a ramp rate of 50 ℃/min and held for 5min to eliminate thermal history. Then rapidly cooling to 25 ℃, finally heating to 200 ℃ at a heating rate of 10 ℃/min, and recording a DSC curve.
The glass transition point and the melting point of the material can be seen by recording the temperature rise curve.
The torque test is an important test means for reflecting the change of the melt thermal stability state of the materials during blending. Therefore, an applicant uses a torque rheometer to examine the torque change condition of a modified PGA material system in the blending process, the testing temperature is set to be 180 ℃, the time is set to be 30 minutes, the material is added in 3 minutes, and the torque rheometer is rapidly closed to blend at the same time point after the material is added, so as to obtain a material torque and time relation graph with the same initial baseline.
In order to further illustrate the present invention, the following examples are provided to describe the modified PGA material having higher processability and the preparation method thereof in detail, but they should not be construed as limiting the scope of the present invention.
In the following examples, the compatibilizer was ADR resin produced by Basff;
example 1
The composite material comprises the following raw materials in percentage by weight: 10 parts of a plasticizer, 80 parts of polyglycolic acid (PGA) having a molecular weight of 30 ten thousand g/mol, and 10 parts of a compatibilizer (epoxy equivalent of 300 and molecular weight of 8000 g/mol);
the plasticizer is a blending material which is obtained by mixing polyvinyl alcohol with alcoholysis degree of 88% and molecular weight of 800g/mol and industrial-grade ethylene glycol according to a mass ratio of 1:1, drying for 6 hours at 65 ℃, and mixing for 30 minutes by using a high-speed mixer;
the materials are extruded by a double screw extruder, the raw materials are mixed for 15min by a high-speed mixer, the obtained mixed material is dried for 14h at the relative humidity of 25% and the temperature of 25-30 ℃, and the obtained mixed material is put into the double screw extruder for granulation after the weight-loss water content is 1.5-2%; the length-diameter ratio of the double-screw extruder at least reaches 1:55, the temperature of the feeding section is kept at about 170 ℃, the temperature of the mixing section is 230 ℃, and the temperature of the extrusion section is kept at about 190 ℃; granulating by underwater granulation, drying the finished master batch at 80 ℃ for 2 hours, packaging with aluminum foil, vacuumizing, and storing in a dry environment.
Table 1 results of property tests of modified PGA prepared in example 1 and raw PGA
As seen from table 1: the processing melting point of the modified PGA is obviously reduced but the glass transition temperature is unchanged, so that the processing performance is improved and the energy consumption is reduced on the premise of ensuring the basic physical and chemical properties of the material. At the same time, the reduction in processing torque allows the PGA to be better compatible with other materials such as PLA, PBAT, etc. during processing.
FIG. 1 is an SEM image of unmodified conventional PGA material blended with PBAT; FIG. 2 is an SEM photograph of a modified PGA prepared in example 1 according to the present invention blended with PBAT, wherein PBAT is a copolymer of butylene adipate and butylene terephthalate in an amount of 30 wt%. As can be seen from a comparison of fig. 1 and 2: the phase size of the modified PGA material is obviously reduced, which shows that the processing property is more excellent.
Example 2
The composite material comprises the following raw materials in percentage by weight: 15 parts of a plasticizer, 75 parts of polyglycolic acid (PGA) having a molecular weight of 35 ten thousand g/mol, 5 parts of a compatibilizer (epoxy equivalent of 280, molecular weight of 10000 g/mol);
the plasticizer is polyvinyl alcohol with alcoholysis degree of 95% and molecular weight of 800g/mol and industrial-grade ethylene glycol according to a mass ratio of 1:1, drying the mixture at 65 ℃ for 6 hours, and mixing the mixture for 30 minutes by using a high-speed mixer to obtain a blended material;
the materials are extruded by a double screw extruder, the raw materials are mixed for 15min by a high-speed mixer, the obtained mixed material is dried for 14h at the relative humidity of 25% and the temperature of 25-30 ℃, and the obtained mixed material is put into the double screw extruder for granulation after the weight-loss water content is 1.5-2%; the length-diameter ratio of the double-screw extruder at least reaches 1:55, the temperature of the feeding section is kept at about 170 ℃, the temperature of the mixing section is 230 ℃, and the temperature of the extrusion section is kept at about 190 ℃; granulating by underwater granulation, drying the finished master batch at 80 ℃ for 2 hours, packaging with aluminum foil, vacuumizing, and storing in a dry environment.
Table 2 results of property tests of the modified PGA prepared in example 2 and the raw PGA
As seen from table 2: the processing melting point of the modified PGA is obviously reduced but the glass transition temperature is unchanged, so that the processing performance is improved and the energy consumption is reduced on the premise of ensuring the basic physical and chemical properties of the material. At the same time, the reduction in processing torque allows the PGA to be better compatible with other materials such as PLA, PBAT, etc. during processing.
Comparative example
The composite material comprises the following raw materials in percentage by weight: 15 parts of plasticizer, 75 parts of polyglycolic acid (PGA) with the molecular weight of 20 ten thousand g/mol and 5 parts of compatilizer, wherein the compatilizer is ethylene acrylic acid copolymer and has the molecular weight of 20000 g/mol;
the plasticizer is dibutyl phthalate;
the materials are extruded by a double screw extruder, the materials are mixed for 15min by a high-speed mixer to obtain a mixed material, the mixed material is dried for 14h at the relative humidity of 25% and the temperature of 25-30 ℃, and the mixed material is put into the double screw extruder for granulation after the weight-loss water content is 1.5-2%; the length-diameter ratio of the double-screw extruder at least reaches 1:55, the temperature of the feeding section is kept at about 170 ℃, the temperature of the mixing section is 230 ℃, and the temperature of the extrusion section is kept at about 190 ℃; granulating by underwater granulation, drying the finished master batch at 80 ℃ for 2 hours, packaging with aluminum foil, vacuumizing, and storing in a dry environment.
Table 3 results of performance test of modified PGA prepared in comparative example and raw PGA
As seen from table 3: the processing melting point of the modified PGA is not obviously reduced, and the processing performance of the material is not greatly improved. Meanwhile, the increase of the processing torque reflects that the processing of the material is more difficult, and the effect of improving the processing is not achieved.
As can be seen from the above examples, the present invention provides a modified PGA material with improved processability, which is prepared from the following raw materials: 5-15 parts of plasticizer, 70-80 parts of polyglycolic acid and 5-25 parts of compatilizer; the molecular weight of the polyglycolic acid is 30-50 ten thousand g/mol; the plasticizer is a mixture of polyvinyl alcohol and ethylene glycol, the molecular weight of the polyvinyl alcohol is 500-800 g/mol, and the alcoholysis degree is 88-95%; the epoxy equivalent of the compatilizer is 280-310 g/mol, and the molecular weight is 8000-10000 g/mol. The invention adopts the specific types of plasticizers and compatilizers to modify the polyglycolic acid, so that the polyglycolic acid has lower melting point and higher processing rheological property; and has better compatibility with other materials.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A modified PGA material with high processability is characterized by being prepared from the following raw materials:
5-15 parts of plasticizer, 70-80 parts of polyglycolic acid and 5-25 parts of compatilizer;
the molecular weight of the polyglycolic acid is 30-50 ten thousand g/mol;
the plasticizer is a mixture of polyvinyl alcohol and ethylene glycol, the molecular weight of the polyvinyl alcohol is 500-800 g/mol, and the alcoholysis degree is 88-95%;
the epoxy equivalent of the compatilizer is 280-310 g/mol, and the molecular weight is 8000-10000 g/mol.
2. The modified PGA material of claim 1, wherein the mass ratio of polyvinyl alcohol to ethylene glycol is 1: 0.9 to 1.1.
3. The modified PGA material of claim 1, wherein the plasticizer is prepared by the following method:
drying polyvinyl alcohol and ethylene glycol at 63-68 ℃ for 5.5-6.5 h, and mixing for 25-35 min to obtain the plasticizer.
4. The modified PGA material of claim 1, wherein the PGA has a melting point of 220 to 230 ℃The glass transition temperature is 38 +/-5 ℃, and the specific gravity is 1.2-1.3 g/cm3。
5. A method for preparing modified PGA material with high processability according to any one of claims 1 to 4, comprising the steps of:
and (3) mixing 5-15 parts of plasticizer, 70-80 parts of polyglycolic acid and 5-25 parts of compatilizer for 30-60 min, and extruding and granulating to obtain the modified PGA material with high processability.
6. The production method according to claim 5, wherein the weight-loss water content of the mixture of the plasticizer, polyglycolic acid, and the compatibilizer is 1.5 to 2%.
7. The method of claim 5, wherein the extrusion granulation has an aspect ratio of greater than 1: 55.
8. the preparation method according to claim 5, wherein the temperature of the feeding section is 165 to 175 ℃, the temperature of the mixing section is 225 to 235 ℃, and the temperature of the extrusion section is 185 to 195 ℃ during the extrusion granulation.
9. The method of claim 5, wherein the extrusion granulation is carried out by underwater granulation.
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| CN113402869A (en) * | 2021-08-11 | 2021-09-17 | 海南赛诺实业有限公司 | PGA modified blown film material and preparation method thereof |
| CN113462138A (en) * | 2021-08-24 | 2021-10-01 | 海南赛诺实业有限公司 | Modified PGA degradable material, preparation method thereof and degradable plastic film |
| CN114015213A (en) * | 2021-11-16 | 2022-02-08 | 广州明晖新材料有限公司 | 3D printing wire modified PGA composite material for full biodegradation and preparation method thereof |
| CN115322538A (en) * | 2021-05-11 | 2022-11-11 | 国家能源投资集团有限责任公司 | Composition for enhanced modified polyglycolic acid, enhanced modified polyglycolic acid material, and preparation method and application thereof |
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| CN114015213A (en) * | 2021-11-16 | 2022-02-08 | 广州明晖新材料有限公司 | 3D printing wire modified PGA composite material for full biodegradation and preparation method thereof |
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